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Investigations into the reactivity of alkynes and sulfur oxides under gold catalysis

Barrett, Matthew (2016)
Ph.D. thesis, University of Birmingham.

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Abstract

Within this thesis sulfur oxides have been reacted under gold catalysis with alkynes allowing access to interesting and novel structures.
The gold catalysed oxyarylation of alkynes with aryl sulfides has been employed, developing conditions for the use of dibenzothiophene-S-oxide as the oxidant for the first time, to enable an efficient way to modify these useful structures. The extension of the methodology allows disubstitution of dibenzothiophenes and a novel oxyarylation-cycloisomerisation cascade. Overall the method showcases very mild conditions and good chemoselectivity.
Secondly a novel gold catalysed reaction of aromatic disulfur oxides with terminal and ester substituted internal alkynes has been developed. Fluorene and naphthalene derived sulfur oxides can be oxidised and functionalised in a single step with a range of terminal alkynes. The transformation successfully exploits rhodium carbene reactivity with alkynes and sulfur oxides.
Finally a large series of alkynyl sulfoxides have been synthesised which can undergo an efficient gold catalysed intramolecular cyclopropanation with an external oxidant affording fused sulfur heterocycles. This work presents the first example of accessing cyclopropanation from an α-diazo sulfoxide, or equivalent. Attempts to access other carbene reactivity modes are discussed as well as the synthesis of highly enantioenriched alkynyl sulfoxides and their treatment under gold catalysis.

Type of Work:Ph.D. thesis.
Supervisor(s):Grainger, Richard S. and Davies, Paul
School/Faculty:Colleges (2008 onwards) > College of Engineering & Physical Sciences
Department:School of Chemistry
Additional Information:

Embargo to 31 July 2018 (2016 PhD)

Subjects:QD Chemistry
Institution:University of Birmingham
ID Code:6556
This unpublished thesis/dissertation is copyright of the author and/or third parties. The intellectual property rights of the author or third parties in respect of this work are as defined by The Copyright Designs and Patents Act 1988 or as modified by any successor legislation. Any use made of information contained in this thesis/dissertation must be in accordance with that legislation and must be properly acknowledged. Further distribution or reproduction in any format is prohibited without the permission of the copyright holder.
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